Provided herein are polishing compositions for removal of Co, for example, selectively over Cu, and methods of their use. A polishing composition comprising an abrasive and one or more Co complexors, where the polishing composition has a pH of 9 or more, and the Co complexor comprises one or more of functional groups selected from phosphonic acid (—P(═O)(OH)2) group or carboxyl (—C(═O)OH) group.
Legal claims defining the scope of protection, as filed with the USPTO.
1. A polishing composition for polishing Co or a Co containing substrate, the composition comprising an abrasive; at least one Co complexor; ammonia; and bicarbonate; wherein the polishing composition has a pH of 9 or more, and the Co complexor comprises at least one selected from a group of 2-Aminoethylphosphonic acid (AEPn), Dimethyl methylphosphonate (DMMP), Tetramethylenediamine tetra(methylene phosphonic acid) (TDTMP), N-(phosphonomethyl)iminodiacetic acid (PMIDA), 2-carboxyethyl phosphonic acid (CEPA), 2-Hydroxyphosphonocarboxylic acid (HPAA), N,N-bis(phosphonomethyl)glycine (glyphosine) (PMG), Iminodimethylenephosphonic acid (IDMP), 2-hydroxyphosphonoacetic acid (HPAA), and amino tri(methylenephosphonic acid) (ATMP) or a salt of each thereof.
2. The polishing composition of claim 1 , wherein the complexor is present in an amount by weight of the polishing composition of less than or equal to 5%.
3. The polishing composition of claim 1 , wherein the abrasive is silica, alumina, or ceria.
4. The polishing composition of claim 1 , further comprising at least one of an oxidizing agent, a surfactant, and a corrosion inhibitor.
5. The polishing composition of claim 4 , wherein the oxidizing agent is present in an amount by weight of the polishing composition of 0.1-4%.
6. The polishing composition of claim 4 , wherein the oxidizing agent is H 2 O 2 .
7. The polishing composition of claim 4 , wherein the corrosion inhibitor is present in an amount by weight of the polishing composition of 0.1-0.4%.
8. The polishing composition of claim 4 , wherein the corrosion inhibitor is benzotriazole (BTA).
9. The polishing composition of claim 4 , wherein the surfactant is present in an amount by weight of the polishing composition of 0.01-2%.
11. A method of polishing, the method comprising polishing Co and optionally Cu with a composition comprising an abrasive and one or more Co complexors, wherein the polishing composition has pH of 9 or more, and the Co complexor comprises one or more of functional groups selected from phosphonic acid (—P(═O)(OH) 2 ) group or carboxylic (—C(═O)OH) group.
12. The method of claim 11 , wherein a removal rate of Co is 200 angstrom/min to 2000 angstrom/min.
13. The method of claim 12 , wherein a removal rate of Cu is less than 100 angstrom/min, or less than 80 angstrom/min.
14. The method of claim 13 , wherein a Co:Cu removal selectivity is 5 or more.
15. The method of claim 11 , wherein the complexor comprises at least one phosphonic acid derivative, the phosphonic acid derivative comprises at least one phosphonic acid (—P(═O)(OH) 2 ) group or a salt thereof each covalently attached independently by a bond or a linker to a core, the core is selected from a heteroatom or a C 1 -C 20 hydrocarbyl moiety, wherein the hydrocarbyl moiety is optionally substituted with 1-5 heteroatoms, optionally substituted with 1-5 hydroxyl groups, or optionally substituted with 1-5 heteroatoms and 1-5 hydroxyl groups, the linker is a divalent or trivalent heteroatom or a divalent or trivalent C 1 -C 20 hydrocarbyl moiety, wherein the hydrocarbyl moiety is optionally substituted with 1-5 heteroatoms, optionally substituted with 1-5 hydroxyl groups, or optionally substituted with 1-5 heteroatoms and 1-5 hydroxyl groups, and the heteroatom is independently selected from N, O, S, P and oxidized forms of N, S, and P.
16. The method of claim 15 , wherein the phosphonic acid derivative further comprises at least one carboxyl group or a salt thereof.
17. The method of claim 16 , wherein the phosphonic acid derivative is a compound of formula (I) or a salt thereof, wherein is the core, each L independently is a bond or a linker, wherein the core and the linker are defined as in claim 15 , each u independently is 0-3, each v independently is 0-3, and y is 1-5; provided that the derivative contains at least one phosphonic acid group or a salt thereof.
18. The method of claim 15 , wherein the core is a heteroatom.
19. The method of claim 15 , wherein the core is a hydrocarbyl moiety selected from alkylenes optionally substituted with 1-3 hydroxyl groups.
20. The method of claim 11 , wherein the complexor comprises at least one selected from a group of 2-Aminoethylphosphonic acid (AEPn), Dimethyl methylphosphonate (DMMP), 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (HEDP), Amino tris(methylene phosphonic acid) (ATMP), Ethylenediamine tetra(methylene phosphonic acid) (EDTMP), Tetramethylenediamine tetra(methylene phosphonic acid) (TDTMP), Hexamethylenediamine tetra(methylene phosphonic acid) (HDTMP), Diethylenetriamine penta(methylene phosphonic acid) (DTPMP), Phosphonobutane-tricarboxylic acid (PBTC), N-(phosphonomethyl)iminodiacetic acid (PMIDA), 2-carboxyethyl phosphonic acid (CEPA), 2-Hydroxyphosphonocarboxylic acid (HPAA), Amino-tris-(methylene-phosphonic acid) (AMP), N,N-bis(phosphonomethyl)glycine (glyphosine) (PMG), Iminodimethylenephosphonic acid (IDMP), and Ethylene Diamine Tetra (Methylene Phosphonic Acid) (EDTPO), and salts thereof.
21. The method of claim 11 , wherein the complexor comprises at least one of citric acid, citric acid salt, ethylenediamine tetraacetic acid (EDTA), 2-hydroxyphosphonoacetic acid (HPAA), and amino tri(methylene phosphonic acid) (ATMP).
22. The method of claim 11 , wherein the complexor is selected from citric acid, a citric acid salt, and EDTA.
23. The polishing composition of claim 1 , wherein the Co complexor comprises 2-Aminoethylphosphonic acid (AEPn), Dimethyl methylphosphonate (DMMP), or Tetramethylenediamine tetra(methylene phosphonic acid) (TDTMP).
24. The polishing composition of claim 1 , wherein the Co complexor comprises N-(phosphonomethyl)iminodiacetic acid (PMIDA), 2-carboxyethyl phosphonic acid (CEPA), or 2-Hydroxyphosphonocarboxylic acid (HPAA).
25. The polishing composition of claim 1 , wherein the Co complexor comprises N,N-bis(phosphonomethyl)glycine (glyphosine) (PMG), Iminodimethylenephosphonic acid (IDMP), 2-hydroxyphosphonoacetic acid (HPAA), or amino tri(methylenephosphonic acid) (ATMP).
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February 27, 2014
February 21, 2017
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